Vulcanizable mixture containing bis-(2-ethylamino-s-triazin-6-yl)-tetrasulfide

ABSTRACT

The invention is directed to bis-(2-ethylamino-4-diethylamino-s-triazin-6-yl)-tetrasulfide and a process for its production from the corresponding mercaptotriazine. The compound of the invention is employed in vulcanizable mixtures as a cross-linker or as vulcanization accelerator.

BACKGROUND OF THE INVENTION

The invention is directed to bis-(2-ethylamino-4-diethylamino-s-triazin-6-yl)tetrasulfide (V 480), a process for its production, its use, and vulcanizable mixtures containing it. The corresponding disulfide is known from German Pat. No. 1,669,954 and the related Westlinning U.S. Pat. No. 3,801,537. The entire disclosure of Westlinning is hereby incorporated by reference and relied upon. The disulfide can be produced for example from the corresponding mercaptotriazine by oxidation with iodine or hydrogen peroxide. The compound thus obtained is employed as a vulcanization accelerator in rubber mixtures.

The problem to be solved by the invention is to find a compound which imparts better properties to vulcanizates and process for the production of the compound.

SUMMARY OF THE INVENTION

The subject matter of the invention is bis-(2-ethylamino-4-diethylamino-s-triazin-6-yl)tetrasulfide (V 480) and a process for its production which comprises reacting an aqueous, alkaline solution of 2-ethylamino-4-diethylamino-6-mercaptotriazine in a 2-phase system with a solution of S₂ Cl₂ in an inert organic solvent at a temperature of <+10° C., with the proviso that the solvent either does not dissolve the tetrasulfide or only slightly dissolves it.

Advantageously there is produced an alkaline aqueous solution of the mercaptotriazine which contains the alkali ions (e.g. sodium or potassium ions) and mercaptotrazine molecule in equimolar amounts.

However, preferably there is used an amount of alkali, especially sodium hydroxide which is about 5 to 10% higher.

This solution is mixed with an organic solvent, especially an aliphatic or cycloaliphatic hydrocarbon, especially benzene (gasoline), petroleum ether or cyclohexane, so that there is formed a 2-phase system and there is added a solution of S₂ Cl₂, preferably in the solvent which also is premixed beforehand with the solvent for the mercaptotriazine. The temperature thereby should be below 10° C., preferably below 5° C.

S₂ Cl₂ is brought to reaction in equimolar amounts under vigorous stirring. Under the stated conditions the S₂ Cl₂ surprisingly acts exclusively in a condensing manner. The molar ratio of S₂ Cl₂ to the mercaptotriazine is preferably from 1:1 to 1,01:1, especially from 1:1 to 1,1:1.

The product which precipitated was separated with the help of commonly known procedures and dried advantageously at 40°-45° C. under a vacuum.

Other subject matter of the invention include the use of V 480 in vulcanizable rubber mixtures and the corresponding V 480 containing mixtures themselves.

In the use of the compound V 480 of the invention as cross-linker or vulcanization accelerator it clearly shows its superiority to the standard compounds as well as to the disulfide V 143.

There is an extensive palatte of accelerators available to the rubber processing industry, especially for sulfur vulcanization, of which the most important classes for all purpose rubbers are: benzthiazolylsulfenamide, bis-benzthiazolyldisulfide, and 2-mercaptobenzothiazole as well as their corresponding triazine derivatives. Besides there is a series of special compounds such as thiuramdisulfides and peroxides which also act as cross-linkers without further additives such as sulfur, but which also are frequently used in combination with sulfur.

Today, the quantitatively most significant in terms of practical use, especially for the vulcanization of all purpose rubbers are the benzthiazolylsulfenamides.

A substantial disadvantage of the just mentiond vulcanization accelerators, especially the sulfenamides, is their greatly increasing tendency to reversion of the vulcanizate with increasing vulcanization temperature, especially when using besides reversion susceptible types of rubber such as NR and polyisoprene. With increasing temperature the speed of reversion increases so greatly that on the one hand there is a drastic reduction of the cross-linking density at optimum vulcanization and on the other hand, there is a sharp decline of the optimum cross-linking density with a frequently unavoidable over vulcanization. This is of similar concern but applies to a lesser extent to the remaining accelerator of the class of benzothiazoles.

These disadvantages of the benzothiazole accelerators limit their usability with increasing vulcanization temperature and places limits in reference to the efforts of the processing industry to increase productivity by the use of higher vulcanization temperatures.

A further non-neglibible disadvantage today, especially of the sulfenamides, is that there is formed free amine during the vulcanization process, which, insofar as they are nitrosizable, can lead to the formation of toxic nitrosamines, which in the future can be expected to limit their areas of use through legislation.

Surprisingly V 480 proves to be a compound both in regard to its use as a cross-linker and also as a vulcanization accelerator in sulfur vulcanization, which imparts to the vulcanizates produced therewith even at high vulcanization temperatures extraordinarily high reversion resistance. Therefore, they are predestined for use with high temperature vulcanization and therewith make possible increases in productivity.

The use of V 480 includes known rubber mixtures according to the state of the art such as natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), isobutylene isoprene rubber (IIR), ethylene-propylene-terpolymer rubber (EPDM), nitrile rubber (NBR), halogen containing rubber (e.g. polychloroprene or chlorinated natural rubber) and especially natural rubber which is epoxidized up to 75% (ENR), as well as their mixtures. The presence of double bonds is essential. The use of V 480 has particular significance of the reversion susceptible isoprene and natural rubbers, as well as their blends with other rubbers, V 480 is employed in sulfur containing rubber mixtures in an amount of 0.3 to 15, preferably 0.3 to 5 parts by weight per 100 parts of rubber.

In sulfur-free rubber mixtures there is used in an amount of 0.3 to 10, preferably, 0.3 to 5 parts by weight of V 480 per 100 parts by weight of rubber.

The rubber mixtures also contain the customary reinforcing system, i.e. furnace blacks, channel blacks, flame blacks, thermal blacks, acetylene blacks, arc blacks, (K blacks etc. as well as synthetic fillers such as silicas, silicates, aluminum oxide hydrate, calcium carbonate, and natural fillers such as clays, siliceous chalks, chalks, talcs, etc, and their blends in an amount of 5 to 300 parts per 100 parts of rubber ZnO and stearic acid as vulcanization promoters in an amount of 2 to 5 parts,

customarily used antiagers, ozone protectants and fatigue protectants such as, e.g. IPPD, TMQ, as well as waxes as light protectants and their blends,

plastizers at pleasure such as e.g. aromatic, naphthenic, parrafinic, synthetic plasticizers, and their blends

optionally retarders such as e.g. N-cyclohexylthiophthalimide, (N-trichloromethylthiophenylsulfonyl)-benzene and their blends,

optionally silanes such as e.g. bis-(3-triethoxysilylpropyl)-tetrasulfide, gamma-chloropropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, ##STR1## and their blends, in an amount of 0.1 to 20, preferably 1 to 10 parts per 100 parts of filler,

optionally sulfur in an amount of 0.5 to 4 parts per 100 parts of rubber,

optionally other customary accelerators customarily employed as secondary accelerators in the rubber industry, especially Vulkalent E, in an amount of 0.2 to 4 parts, preferably 0.6 to 1.8 parts based on 100 parts of rubber, optionally additional sulfur donors, optionally dyes and processing aids.

The vulcanizable composition can contain 0.3 to 15 parts of V 480 and also contain (N-trichloromethylthiophenylsulfonyl)-benzene in a 1:1 molar ratio to the V 480 and sulfur in an amount of 0.2 to 4 parts based on 100 parts of the rubber.

The area of use extends to rubber mixtures, as they are customarily used in making tires, to industrial articles, such as e.g. mixtures for conveyor belts, V-belts, molded articles, piles with or without insertions, rubber rolls, linings, spray profiles, freehand articles, films, shoe soles and uppers, cables, full gum tires, and their vulcanizates.

Unless otherwise indicated all parts and percentages are by weight.

The compositions can comprise, consist essentially of, or consist of the stated materials and the process can comprise, consist essentially of, or consist of the recited steps with such materials.

While V 480 can be used with advantage in high temperature vulcanization it also can be used with conventional lower temperature vulcanization.

DETAILED DESCRIPTION EXAMPLE 1

454 grams of 2-diethylamino-4-ethylamino-6-mercaptotriazine were dissolved in aqueous sodium hydroxide which had been produced from 84 grams of NaOH and ≠1.5 liters of water.

The solution was placed in a liter three-neck flask, then there was added 1.5 liters of light benzine (B.P. 80°-110° C.) and the mixture cooled to 0° C. with vigorous stirring.

There was then run in within 20 minutes a solution of 137 grams of S₂ Cl₂ in 100 ml of benzine whereby care was taken that the temperature did not exceed +50° C.

The tetrasulfide immediately precipitated out. At the end of the reaction the mixture was stirred for a further 5 minutes, subsequently sucked off and washed.

The snow white of fine powder was dried in a vacuum/12 Torr at 40°-45° C. Amount: 499.5 grams, corresponding to 97.1% of theory; M.P. 149°-150° C.

Analysis: Bis-(2-Ethylamino-4-diethylamino-s-triazine-6-yl)tetrasulfide, Mol-Wt. 516, C₁₈ H₃₂ N₁₀ S₄

    ______________________________________                                                    C    H          N      S                                            ______________________________________                                         Calculated   41.9   6.2        27.1 24.8                                       Found        41.8   6.5        26.8 24.8                                       ______________________________________                                    

Testing Standards

The physical tests were carried out at room temperature according to the following standard specification (DIN stands for German Industrial Standard):

    ______________________________________                                         Tensile strength, elongation at                                                                    DIN 53504 MPa                                              break and on 6 mm thick                                                        rings modulus                                                                  Resistance to tear  DIN 53507 N/mm                                             propagation                                                                    Impact elasticity   DIN 53512 %                                                Shore A hardness    DIN 53505 --                                               Mooney Test, ML 4   DIN 53524 --                                               Goodrich Flexometer ASTM      °C.                                       (Determination of heat                                                                             D 62362                                                    build-up ΔT)                                                             Firestone - Ball Rebound                                                                           AD 20245                                                   ______________________________________                                    

In the use examples there are employed the following names and abbreviations whose meanings are given below:

    ______________________________________                                         RSS:             Ribbed Smoked Sheet                                                            (natural rubber)                                              Corax.sup.R N 220:                                                                              Carbon Black, Surface                                                          Area (BET) 120 m.sup.2 /g                                                      (Degussa)                                                     Naftolen ZD:     Hydrocarbon Plasticizer                                       Ingralen 450:    Aromatic hydrocarbon                                                           plasticizer                                                   Ingroplast NS:   Naphthenic hydrocarbon                                                         plasticizer                                                   Vulkanox 4010 NA:                                                                               N--Isopropyl-N'--phenyl-                                                       p-phenylene-diamine                                           Vulkanox HS:     Poly-2,2,4-trimethyl-1,                                                        2-dihydroquinoline                                            Mesamoll:        Alkylsulfonic acid ester                                                       of phenyl and cresol                                          Protektor G35:   Wax protector against                                                          ozone                                                         Vukacit MOZ:     N--Morpholine-2-benzo-                                                         thiazolsulphenamide                                           Vulcacit Mercapto:                                                                              2-Mercaptobenzothiazole                                       Vulcacit Thiuram:                                                                               Tetramethyl-thiurammono-                                                       sulfide                                                       Vulcazit CZ:     N--Cyclohexyl-2-benzo-                                                         thiazolesulphenamide                                          Vulcalent E:     (N--trichloromethylthio-                                                       phenylsulfonyl)-benzene                                       PVI:             N--Cyclohexylthiophthal-                                                       imide                                                         Ultrasil VN3:    Precipitated silica                                                            (Degussa)                                                     Gran.:           Granulate                                                     V143:            Bis-(2-Ethylamino-4-di-                                                        ethylamino-s-triazine-                                                         6-yl)-disulfide                                               ______________________________________                                    

EXAMPLE 2 Reversion Stability With V 480 As Cross-Linker (Carbon Black As Filler)

    ______________________________________                                                        1       2       3                                               ______________________________________                                         RSS 1, Ml 4 = 67 100       100     100                                         CORAX N 220      50        50      50                                          ZnO RS           5         50      5                                           Stearic acid     2         2       2                                           Naftolen ZD      3         3       3                                           Vulkanox 4010 NA 2.5       2.5     2.5                                         Vulkanox HS      1.5       1.5     1.5                                         Protektor G 35   1         1       1                                           Vulkacit MOZ     1.43      --      --                                          V 143            --        1.29    --                                          PVI              --        0.4     --                                          V 480            --        --      4                                           Sulfur           1.5       1.5     --                                           ##STR2##                                                                      170° C.   30.0      8.5     2.3                                         ______________________________________                                    

The example shows that reversion stability was obtained using V 480 without sulfur. As reference systems there were used in mixture 1 MOZ in a so-called semi-efficient dosing, which according to the state of the art has been evaluated as very good and in sample 2 there was used the already reversion stable accelerator V 143.

EXAMPLE 3 Temperature Dependence Of The Reversion Behavior Using V 480 (Carbon Black/Silica As Fillers)

    ______________________________________                                                        4       5       6                                               ______________________________________                                         RSS 1, ML 4 = 67 100       100     100                                         CORAX N 220      25        25      25                                          Ultrasil VN 3 B Gran.                                                                           25        25      25                                          ZnO RS           5         5       5                                           Stearic acid     2         2       2                                           Naftolen ZD      3         3       3                                           Vulkanox 4010 NA 2.5       2.5     2.5                                         Vulkanox HS      1.5       1.5     1.5                                         Protektor G 35   1.5       1.5     1.5                                         V 480            --        --      3                                           Vulkacit MOZ     1.43      --      --                                          V 143            -         1.29    --                                          Sulfur           1.5       1.5     --                                           ##STR3##                                                                      145° C.   22.4      11.3    0                                           160° C.   38.8      20.9    0                                           170° C.   47.4      30.3    1.9                                         180° C.   52.6      38.7    4.6                                         ______________________________________                                    

Mixtures in which carbon black is partially replaced by silica are especially susceptible to reversion. Mixture 6 shows that V 480 used as a cross-linker, i.e., without sulfur, imparted to the vulcanizate even at the highest vulcanization temperatures the utmost resistance to reversion.

EXAMPLE 4 Vulcanization Stability With Overheating At 170° C. Using V 480

    ______________________________________                                                      7        8        9                                               ______________________________________                                         RSS 1, ML 4 = 67                                                                              100        100      100                                         CORAX N 220    25         25       25                                          Ultrasil Un 3 Gran.                                                                           25         25       25                                          ZnO RS         5          50       5                                           Stearic acid   2          2        2                                           Naftolen ZD    3          3        3                                           Vulkanox 4010 NA                                                                              2.5        2.5      2.5                                         Vulkanox HS    1.5        1.5      1.5                                         Protektor G 35 1          1        1                                           Vulkacit MOZ   1.43       --       --                                          V 143          --         1.29     --                                          V 480          --         --       3                                           Sulfur         1.5        1.5      --                                           ##STR4##                                                                      170° C. 44.7       28.7     2.6                                         Vulcanization time        *t.sub.95%                                           at 170° C.         t.sub.95%+50'                                        Tensile Strength                                                                              17.2       16.0     19.3                                                       12.5       11.2     19.7                                        Modulus 300%   5.1        3.7      5.5                                                        3.3        2.8      5.3                                         Tear Propagation                                                               Resistance     32         16       29                                                         6          5        28                                          Firestone-Ball Rebound                                                                        54.9       52.8     53.5                                                       51.3       51.7     53.2                                        ______________________________________                                          *t.sub.95% means that 95% of the vulcanization agent had been reached;         t.sub.95%+50'   means that it was heated for a further 50 minutes.       

This example shows that with increasing reversion with overheating, namely 50'/170° C. a greater decrease occurs in the physical vulcanization data. This can be seen especially clearly with mixture 7 in the tensile strength and 300% Modulus as well as in the resistance to tear propagation while in contrast mixture 9 in overheating the physical data remained practically unchanged.

Here also V 480 was compared to a semi-EV-system, which according to the state of the art already had been distinguished as resistant to reversion.

EXAMPLE 5 Reversion Stability Using V 480 As Accelerator At a Vulcanization Temperature of 170° C.

    ______________________________________                                                           10    11                                                     ______________________________________                                         RSS 1, ML 4 = 67    100     100                                                CORAX N 220         50      50                                                 ZnO RS              5       5                                                  Stearic acid        2       2                                                  Naftolen ZD         3       3                                                  Vulkanox 4010 NA    2.5     2.5                                                Vulkanox HS         1.5     1.5                                                Protektor G 35      1       1                                                  Vulkacit MOZ        --      1.43                                               V 480               1.5                                                        Sulfur              0.8     1.5                                                 ##STR5##           0.8     29.2                                               Tensile Strength    22.6    24.3                                               Modulus 300%        11.0    10.4                                               Elongation at Break 480     530                                                Firestone-Ball Rebound                                                                             46.5    45.9                                               Shore A Hardness    62      62                                                 ______________________________________                                    

Example 5 shows that the combination of 1.5 parts V 480 with 0.8 parts sulfur always remain completely resistant to conversion at 170° C. compared to the corresponding sulfenamide and that with this combination at t_(95%) practically the same data level is established.

EXAMPLE 6 Influence Of The Sulfur Dosing On The V 480 Accelerator (Vulcanization Temperature: 170° C.)

    ______________________________________                                                      12   13     14     15   16   17                                   ______________________________________                                         RSS 1, Ml 4 = 67                                                                              100    100    100  100  100  100                                CORAX N 220    50     50     50   50   50   50                                 ZnO RS         5      5      5    5    5    5                                  Stearic acid   2      2      2    2    2    2                                  Naftolen ZD    3      3      3    3    3    3                                  Vulkanox 4010 NA                                                                              2.5    2.5    2.5  2.5  2.5  2.5                                Vulkanox HS    1.5    1.5    1.5  1.5  1.5  1.5                                Protektor G 35 1      1      1    1    1    1                                  Vulkacit MOZ   1.43   --     --   --   --   --                                 V 143          --     1.29   --   --   --   --                                 PVI            --     0.4    --   --   --   --                                 V 480          --     --     1.5  1.5  1.5  1.5                                Sulfur         1.5    1.5    0.8  1    1.2  1.4                                 ##STR6##      26.8   6.9    2.4  3.4  4.1  4.6                                t.sub.10%      3.8    4.2    3.1  2.9  2.9  2.8                                t.sub.80 -t.sub.20%                                                                           1.4    1.4    1.6  1.6  1.5  1.5                                Vulcanizate data at                                                                           11.5   12.1   11.4 12.1 12.5 13.1                               t.sub.95% Modulus 300%                                                         Shore Hardness 63     66     63   63   64   65                                 ______________________________________                                    

Example 6 shows that an increase of sulfur content beyond 0.8 is possible and leads to increase in modulus without reversion increasing very greatly. Indeed the raising of the sulfur content results in a slight shortening of the scorch properties. This can be counterbalanced through the use of Vulkalent E (see Example 7).

EXAMPLE 7 Effect Of Customary Retarders On The Pre-Vulcanization Time And Reversion Employing V 480

    ______________________________________                                                        18   19      20      21                                         ______________________________________                                         RSS 1, ML (1 + 4) = 67                                                                          100    100     100   100                                      CORAX N 220      50     50      50    50                                       ZnO RS           5      5       5     5                                        Stearic acid     2      2       2     2                                        Naftolen ZD      3      3       3     3                                        Vulkanox 4010 NA 2.5    2.5     2.5   2.5                                      Vulkanox HS      1.5    1.5     1.5   1.5                                      Protektor G 35   1      1       1     1                                        Vulkacit MOZ     1.43   --      --    --                                       V 480            --     1.5     1.5   1.5                                      Sulfur           1.5    0.8     0.8   0.8                                      PVI              --     --      1.2   --                                       Vulkalent E      --     --      --    1.2                                      Scorch time 130° C. min                                                                  21.5   8.0     17.5  21.0                                     (increase 2 scale                                                              divisions                                                                      Scorch at 170° C.                                                                        3.8    2.8     3.8   4.1                                      (t.sub.10%)                                                                    Modulus 300%     10.6   11.0    8.8   13.7                                     ______________________________________                                    

EXAMPLE 8 Prolongation Of Scorch And Increase In Modulus Of V 480/Vucalent E--Combination

    ______________________________________                                                    22    23      24      25    26                                      ______________________________________                                         RSS 1, M1 4 = 67                                                                            100     100     100   100   100                                   CORAX N 220  50      50      50    50    50                                    ZnO RS       5       5       5     5     5                                     Stearic acid 2       2       2     2     2                                     Naftolen ZD  3       3       3     3     3                                     Vulkanox 4010 NA                                                                            2.5     2.5     2.5   2.5   2.5                                   Vulkanox HS  1.5     1.5     1.5   1.5   1.5                                   Protektor G 35                                                                              1       1       1     1     1                                     Vulkacit MOZ 1.43    --      --    --    --                                    V 480        --      1.5     1.5   1.5   1.5                                   Vulkalent E  --      --      0.4   0.8   1.2                                   Sulfur       1.5     0.8     0.8   0.8   0.8                                   Scorch time 130° C.,                                                                 21.5    8.0     12.5  16.7  21.0                                  Min. (increase 2                                                               scale divisions)                                                               Scorch time 170° C.                                                                  3.8     2.8     3.1   3.7   4.1                                   (t.sub.10%), min.                                                              Modulus 300% 10.6    11.0    11.8  12.7  13.7                                  ______________________________________                                    

EXAMPLE 9 Prolongation Of The Prevulcanization Time By Vulkalent E With The V 480 Vulcanization

    ______________________________________                                                        27   28      29      30                                         ______________________________________                                         RSS 1, ML (1 + 4) = 67                                                                          100    100     100   100                                      CORAX N 220      25     25      25    25                                       Ultrasil VN3 Gran.                                                                              25     25      25    25                                       ZnO RS           5      5       5     5                                        Stearic acid     2      2       2     2                                        Naftolen ZD      3      3       3     3                                        Vulkanox 4010 NA 2.5    2.5     2.5   2.5                                      Vulkanox HS      1.5    1.5     1.5   1.5                                      Protektor G 35   1      1       1     1                                        Vulkacit MOZ     1.43   --      --    --                                       PVI              --     --      1.2   --                                       V 480            --     3       3     1.5                                      Vukalent E       --     --      --    1.2                                      Sulfur           1.5    0.8     0.8   0.8                                      Scorch time 130° C.,                                                                     29.5   16.1    28.5  30.0                                     Min (increase 2                                                                scale divisions)                                                               Scorch time 170° C.                                                                      4.5    3.6     4.2   4.7                                      Modulus 300%     5.3    6.4     6.4   8.6                                      ______________________________________                                    

Example 9 shows the effectiveness of the retarder Vulkalent E in the case of a blend of carbon black and silica. Using 1.5 parts V 480, 0.8 parts sulfur and 1.2 parts of Vulkalent E there were obtained MOZ prevulcanization times without further doing anything. The reversion properties of V 480 vulcanization also were not negatively influences by the inclusion of retarders, no more than were the physical data of the vulcanizate.

EXAMPLE 10 V 480 As Accelerator In SBR

    ______________________________________                                                        31      32      33                                              ______________________________________                                         SBR 1712         137.5     137.5   137.5                                       CORAX N 339      60        60      60                                          ZnO RS           3         3       3                                           Stearic acid     2         2       2                                           Protektor G 35   1         1       1                                           Vulkanox 4010 NA 1.5       1.5     1.5                                         Vulkacit D       0.5       0.5     --                                          Vulkacit CZ      1.45      --      --                                          V 480            --        1.5     1.5                                         Sulfur           1.6       1.5     1.5                                          ##STR7##        10.5      7.3     8.3                                         at 165° C.                                                              Tensile Strength 20        19.2    23.1                                        Modulus 300%     10.1      11.4    10.9                                        Elongation at Break                                                                             480       430     460                                         Shore A Hardness 63        65      64                                          ______________________________________                                    

Example 10 shows that V 480 also exerts a positive influence on the resistance to reversion in otherwise already reversion resistant SBR mixtures.

EXAMPLE 11 Resistance To Reversion Of SBR-Vulcanization With V 480

    ______________________________________                                                            33    34                                                    ______________________________________                                         SBR 1500             100     100                                               CORAX N 220          50      50                                                ZnO RS               5       5                                                 Stearic acid         2       2                                                 Naftolen ZD          3       3                                                 Vulkanox 4010 NA     2.5     2.5                                               Vulkanox HS          1.5     1.5                                               Protektor G 35       1       1                                                 Vulkacit CZ          1.5     --                                                V 480                --      1                                                 Sulfur               1.8     1.8                                                ##STR8##            12.1    9.1                                               Vulcanizate data at t.sub.95% :                                                Tensile Strength     20.2    21.8                                              Modulus 300%         10.6    11.1                                              Elongation at Break  450     460                                               Resistance To Tear   13      14                                                Propagation                                                                    Shore A Hardness     63      64                                                ______________________________________                                    

This sample shows that V 480 still further improves the reversion properties of the otherwise already slightly reversion susceptible SBR 1500.

EXAMPLE 12 V 480 In Perbuban (Nitrile Rubber)

    ______________________________________                                         Perbunan N 3307 NS   100     100                                               CORAX N 220          50      50                                                ZnO RS               5       5                                                 Stearic acid         1       1                                                 Ingralen 450         5       5                                                 Mesamoll             10      10                                                Vulkacit CZ          1.3     --                                                V 480                --      1.5                                               Sulfur               1.8     1.8                                                ##STR9##            9.5     6.9                                               Vulcanizate data:                                                              Tensile Strength     19.5    18.8                                              Modulus 300%         9.2     11.3                                              Elongation at Break  480     380                                               Shore A Hardness     64      65                                                ______________________________________                                    

As the example shows the inclusion of V 480 in place of a sulfenamide imparts further advantages in regard to resistance to reversion.

EXAMPLE 13 V 480 In EPDM

    ______________________________________                                         Buna AP 541          100     100                                               CORAX N 220          50      50                                                ZnO RS               5       5                                                 Stearic acid         1       1                                                 Ingraplast NS        10      10                                                Vulkacit Thiuram     1       --                                                Vulkacit Mercapto    0.5     --                                                V 480                --      2.5                                               Sulfur                       1                                                  ##STR10##           3.3     0                                                 Vulcanizate Data:                                                              Tensile Strength     16.0    16.0                                              Modulus 300%         14.4    14.0                                              Elongation at Break  320     350                                               Shore A Hardness     72      69                                                ______________________________________                                    

For EPDM also through the inclusion of V 480 there results at the same regulation of the vulcanizate data the possibility still for further increase of the resistance to reversion.

EXAMPLE 14 Simultaneous Use Of V 480 And Si 69

    ______________________________________                                         RSS 1, ML 4 = 67     100     100                                               CORAX N 220          50      50                                                ZnO RS               5       5                                                 Stearic acid         2       2                                                 Naftolen ZD          3       3                                                 Vulkanox 4010 NA     2.5     2.5                                               Vulkanox HS          1.5     1.5                                               Protektor G 35       1       1                                                 Vulkacit MOZ         1.43    --                                                V 480                --      1.5                                               Si 69                --      1.5                                               Sulfur               1.5     0.4                                                ##STR11##           29.7    0                                                 Vulcanizate data:                                                              Tensile Strength     25.1    22.0                                              Modulus 300%         10.2    10.8                                              Firestone-Ball Rebound                                                                              45.2    44.2                                              Shore A Hardness     63      62                                                Goodrich-Flexometer  159     136                                               delta T Center °C.                                                      ______________________________________                                    

If there is replaced a portion of the sulfur (0.8 parts) by sulfur donors as for example polysulfidic silane, there likewise result an extraordinarily reversion resistance by the example above. Furthermore, there occurs an extraordinary lowering of the build up of heat.

EXAMPLE 15 V 480 Cross-Linking Of Epoxidized Natural Rubber Using Carbon Black And Silica As Filler

    ______________________________________                                                            1    2                                                      ______________________________________                                         ENR 50               100    100                                                CORAX N 330          25     25                                                 Ultrasil VN 3 Gran.  25     25                                                 ZnO RS               5      5                                                  Stearic acid         2      2                                                  Vulkanox HS          2      2                                                  V 480                --     3                                                  Vulkacit MOZ         2.4    --                                                 Vulkacit Thiuram     1.6    --                                                 Sulfur               0.3    0.3                                                Tensile strength     15.1   15.6                                               Modulus 100% (MPa)   8.4    11.0                                               Further Tear Propagation                                                                            8      8                                                  DIN 53 507 (N/mm)                                                              Shore A Hardness                                                               DIN 53 505 23° C.                                                                            82     89                                                 ______________________________________                                    

EXAMPLE 16 V 480 Cross-Linking Of Epoxidized Natural Rubber Using Carbon Black Files

    ______________________________________                                                            1    2                                                      ______________________________________                                         ENR                  100    100                                                CORAX N 220          50     50                                                 ZnO RS               5      5                                                  Stearic acid         2      2                                                  Vulkanox HS          2      2                                                  V 480                --     4                                                  Vulkacit MOZ         2.4    --                                                 Vulkacit Thiuram     1.6    --                                                 Sulfur               0.3    0.3                                                Tensile Strength DIN 18.7   27.0                                               53 504 Ring 1 (MPa)                                                            Modulus 300% (MPa)   18.0   19.0                                               Resistance to further                                                                               12     12                                                 propagation DIN 53 507                                                         (N/mm)                                                                         Shore A Hardness     75     80                                                 DIN 53 505 23° C.                                                       ______________________________________                                     

What is claimed is:
 1. A vulcanizable composition comprising bis-(2-ethylamino-4-diethylamino-s-triazin-6-yl)-tetrasulfide as an accelerator and a vulcanizable rubber selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber, isobutylene-isoprene rubber, ethylene-propylene terpolymer rubber, nitrile rubber, halogen containing rubber, and natural rubber which is epoxidized up to 75%, the amount of triazinyl tetrasulfide being 0.3 to 15 parts based on 100 parts of the rubber.
 2. A sulfur(S₈)-free vulcanizable composition comprising bis-(2-ethylamino-4-diethylamino-s-triazin-6-yl)-tetrasulfide as a cross-linker and a vulcanizable rubber selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber, isobutylene-isoprene rubber, ethylenepropylene terpolymer rubber, nitrile rubber, halogen containing rubber, and natural rubber which is epoxidized up to 75%, the amount of triazinyl tetrasulfide being 0.3 to 10 parts based on 100 parts of rubber.
 3. A vulcanizable composition comprising bis-(2-ethylamino-4-diethylamino-s-triazin-6-yl)-tetrasulfide as an accelerator, at least one member of the group consisting of an additional accelerator, a retarder and an organosilane and a vulcanizable rubber selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber, isobutyleneisoprene rubber, ethylene-propylene terpolymer rubber, nitrile rubber, halogen containing rubber, and a natural rubber which is epoxidized up to 75%, the amount of triazinyl tetrasulfide being 0.3 to 15 parts based on 100 parts of rubber.
 4. The product obtained by vulcanizing the composition of claim
 1. 5. The composition according to claim 1 wherein the rubber is natural rubber.
 6. The product obtained by vulcanizing the composition of claim
 2. 7. A vulcanizable composition according to claim 1 containing (N-trichloromethylthiophenylsulfonyl)-benzene, the molar ratio of the triazinyl tetrasulfide to the phenylsulfonylbenzene being 1:1 and the amount of sulfur being 0.2 to 4 part based on 100 parts of the rubber.
 8. A vulcanizable composition according to claim 7 containing 0.6 to 1.8 parts of sulfur per 100 parts of rubber.
 9. A vulcanizable composition according to claim 2 wherein the rubber is natural rubber.
 10. A vulcanizable composition according to claim 1 wherein the rubber is styrene-butadiene rubber.
 11. A vulcanizable composition according to claim 1 wherein the rubber is nitrile rubber.
 12. A vulcanizable composition according to claim 1 wherein the rubber is ethylene-propylene terpolymer rubber. 